Process of transforming mineral oils.



A. S. RAMAGE.

PROCESS OF TRANSFORMING MINERAL OILS.

APPLICATION FILED APR.27.1916.

, 1,224,787. Patented May 1, 191 7.

l C E w sum/"m VI I 6i v f sratrris PAT NT OFFICE.

awn 8. men, or izurraorr,v moment, nssrenon r ros'rm imam:-

- Be it known that I, Annxanonn' Sr Ramon,

' residing at Detroit, in the county of Wayne ING To all whom it mayconcern: I

a subject of the King of "Great Britain,

and State of Michigan, have invented certain' new and usefulImprovements in Proc esses' of Transforming Mineral Oils, of

' which the following is a specification.

My invention is a process whereby hydrocarbons are transformed, byrestricted oxidation efl'ected through the. agency of a suitablereducible metallic oxid, into other hydrocarbons containingproportionately pinene and limonene;

drocarbons of the benzol type. I Presumably" lesshydrogemwater beingproduced in the reaction. According to my invention I am enabledto'transfor'm paraflin hydrocarbons into olefins, as for example pentaneinto amylene, etc.; or into terpenes such ;as

the formation of olefins, terpenes and aromatic hydrocarbons representsthe successive stages inthe restricted oxidation of a par aflin, so thateach of these groups may con-.

veniently be regarded as derived from the precedinggroup richer inhydrogen, by res moval of a portion only'of this hydrogen.

.On this 'assum tion some of the reactions I involved might e thusexpressed,us1ng gen- 80 eralized formulaazp (1) Conversion of a parafiininto anolefin (2) Conversion'of an olefin into a terpene i (3)Conversion of a ,terpene into an aro A matic hydrocarbon theintermediate reaction stages, if such O1 (5) Conversion of an olefininto an aromatic body 2lt+ n gn +3H O. v Similarly anequation. maybewritten to each case an oxidation of a or into aromatic 'hy-' may withequal propriety be recourm, or nnrnorr, KICIIIGAN, a conroiwrron orimminent.

income or ramsronme man. ons.

Patented May 1, 1 917."

11 into a-terpene (6) 'C,,H,.,.,,' 1 30= C H 3H,O.. In the practice ofmy process, at least reflpreseat the direct transformation of a parwhencarried out under conditionssubstan tiaily as specified below, there isreason to believe that the reaction does in fact occur in successivestages, inasmuch as I usually find among the reaction productsrepresenta tlves of, most or all of the above-mentioned oups (olefins,"terpenes' and aromatic odies).

It will be observed that there occurs in ortion only of the hydro encomponent. 0 the hydrocarbon, Where y a hydrocarbon of any given series(paraflin, olefin" or terpene) is transformed or converted into ahydrocarbon or hydrocarbons of a series relatively poorer in hydrogen.Another product of this restricted oxidation is in each case water, and

J the amount of water produced, relative to' the amount of h drocarbontreated .is an accurate index 0 the extent to which the oxidation hasprogressed. Therefore by 001- lecting the water of oxidation anddetermining its quantity I am enabled definitely to control thereaction. I

I accomplish the results above set forth by subjecting a hydrocarbon, orusually a mixture, of hydrocarbons, torestricted oxidation by areducible metallic oxid, under conditions of temperature and time whichare carefully regulated according to the oxid used, the character of thehydrocarbon'to transformed, and the nature of the products desired. Inthe preferred embodiment of my invention, the hydrocarbon, in a stateofvapor, is caused to pass over or through a bed of reducible oxidcontained in a tube,

v retort or other chamber which may be heated by a'burner or by means ofan electric resistance coil. The temperature within the tube ismaintained, by suitable regulating devices, at a point which issuflicient for the reduction of the oxid in question: and the I time andtemperature are regulated with reference to the yield of water in orderto produce the particular hydrocarbon or hydrocarbon mixture desired.

As reducible oxids suitable 'for my purnickel, cobalt and iron, the lastmentioned poses, I may mention the oxids of copper, no

0.) and the reaction is extremely rapid and not readily controlled.

Using ferric oxid (Fe O a temperature range of 580-750 0. is suitable.Within these limits, provided a sufiicient excess of iron oxid bepresent, no appreciable separation of carbon has been observed. Athigher temperatures, or if the reduction of the OXld is carried too far,crackin sets in and the reduced metal contains car on.

Ferric oxid employed as above undergoes successive reduction to F8 0,,FeO and metal. For the best operating conditions it is preferred toarrest the treatment when the charge in the tube or retort has beenlargely reduced to ferrous oxid FeO, containing usually some iron. Thereduced charge may be regenerated by blasting it with steam whilemaintaining a temperature of approximately 750 0., without removing itfrom the tubes. generation hydrogen is produced, which may be collectedand utilized for hydrogenation, or for other purposes. In case hydrogenis not desired the regeneration may be accomplished by means of air or amixture of air and steam.

Between the approximate temperature limits above mentioned (580750 0.) I

. effect a careful adjustment between the temperature of the oxid andthe boiling-point of the hydrocarbon to be transformed. Thus for ahydrocarbon fraction boiling between 150 and 200 0., the lowertemperature ranges, say 580 to 625 0., are used; whereas for a fractionboiling between 250 and 300 0., the higher temperature ranges, saybetween 700 and 750 0., are used; the intermediate fractions requiringintermediate temperatures for the best results. In practice theboiling-point of the material under treatment is observed and thetemperature of the oxid regulated accordingly:

or example, when treating an oil fraction of which the boiling-point11SeS progressively, the temperature of the oxid is progressively andcorrespondingly increased.

It will be apparent from the foregoing that the precise workingconditions of the process may vary within somewhat wide limits,according, to the character of the Hydrocarbon to e transformed, thenature of the product or products desired, and the specific reducibleoxid used. I will therefore describe my invention by reference to onespecific illustrative example thereof, it being understood that'theinvention is not limited to the mani ulative features detailed in thisexample.

Example: The material treated was a complex hydrocarbon mixtureconsisting largely of olefins and containing constituents boiling allthe way from 150 to 300 '0. The

reaction vessel consisted of a malleable iron tube three feet six incheslong by four inches In the course of this re-- from which it isdelivered by in diameter, electrically heated by nichrome Wire set inalundum cement, a rheostat being provided for accurate control of thetemperature. The tube was'filled with a pure iron oxid of paint grade,prepared from copperas the tube being nearly filled with the ungroundmaterial, in lump and powder form. The temperature was measured by meansof a thermocouple on the outside of the tube which had previously beencalibrated with a thermocouple in the center of the oxid, so that thetemperatures mentioned are, internal.

The oil was vaporized, and the vapors carried through the tube anddischarged into a condensing system. At the beginning of the operationthe temperature reading was 580 0., for a boiling-point of thehydrocarbon introduced of 150 0., and this temperature was graduallyincreased in proportion to the rising boiling-point of the hydrocarbonto an ultimate temperature of 750 0. The pressure within the system wassufiicient only to maintain the regulated flow of the vaportherethrough. The condensate amounted to upward of ninety per cent. ofthe oil treated. Of the recovered product forty-seven per cent. boiledunder 180 0. The remaining high-boiling material was refluxed to beagain subjected to oxidation.

The material boiling 'under 180 C. was fractionated, yielding a seriesof fractions .as follows 7 Up to (3., about 7%, largely 'amyleue.

150 180 0., 25-30%, of which approximately v18% was llmonene, thebalance largely olefins and aromatic hydrocarbone.

. Practically no paraflins were discoverable m the reactlon products,which are therefore very readily purified in order to. recover.

thelr-values. For the purpose for example of recovering benzol andtoluol, it is merely necessary to remove the olefins by the usualtreatment with sulfuric acid leaving the aromatic compounds in excellentcondition for rectification.

A suitable apparatus for carrying out the process is diagrammaticallyshown in the accompanying. drawing, and comprises. a tank 1 forcontaining ,the starting material pipe 2 to a nozzle 3, by pressure uponthe hquid in the tank 1 supplied b a suitable air-compressor 4. .Thehydrocar on is thus injected into a series of connected tubes 6containing the reducible oxid these tubes being mounted in a suitablefurnace F and heated in the arrangement shown by a burner 7. From thetubes 6, a pipe 8 leads to a reflux condenser 9, maintamed at a suitabletemperature From this condenser the residualthrough pipe 14 to thenozzle of an injector 15, supplied with wash-oil (which ma be someheavier paraflin oil or kerosene, oiling-point 180-200 0.), through thepipe sprayed into a chamber 18,

through trapped pipe to the collecting I main 21. The vapors and gasespass from chamber 18 through pipe 22to atower 23, provided with a seriesof perforated plates, the separated liquid passmg through pipe 24 to themain '21. The gases from tower 23 pass 'throu h pipe 25 to a fbelltower- 26, from-,whic the separated liquidspass through pipe 27 to main21. The gases, princl ally hydrogen, pass through'ipipe 28, ed with asuitable gas meter G,vto a gas-holder 29, from which they may be carriedto the burner? through the pipe 30.

The wash oils and condensates recovered from, main 21 may be re-used,preferably a after fractioning off the light products, and

' gressively raising the temperature .of the are returned'to tank 17.

The references in certain claims to the introduction of thehydrocarbonin-a state of vapor snbstantially'unmixed with reactive oxygen isintended to indicate that the hydrocarbon vapors entering the retortsare substantially undiluted by air, steam or oxygen in any otherreactive form, whereby the oxidizing efl'ect to which the vapors aresubjected is essentially or substantially that of the reducible metallicoxid. I

'action products hydroc-ar 1'. The process of transforming hydroecarbons into other hydrocarbons relatively poorer in h drogen, whichconsists in bringing the hy rocarbon to be transformed,'in a state ofvapor substantially unmixed with reactive oxygen, into 'contact'with areduci- 'ble metal oxid, andso regulating the temperature of said oxidand the time of .con-.

tact of the vapor therewith as 'to oxidize a part only of the hydrogencomponent of the hydrocarbon, producin ons relatively poorer inhydrogen, and steam. I

' 2. The process of transforming hydrocar-- hydrocarbons relatively.

bons into other poorer in hydrogen, which consists in bringing thehydrocarbon to be transformed, in a state of vapor substantially unmixedwith reactive oxygen, into contact with iron oxid 'at a temperature of580-750. C., and so regulating the time .of contact between the vaporand the oxid as to oxidize a portion the condensate being collectedfrom' the tank 17. This wash oil is.

rovided withthe separated liquid passing and'olefins into terpenes, andaromatic hy- II 7 temperature of the oxid in correspon thereby as .re- Ireduction of the oxid,

onlg laof the hydrogen component of the h'yd rbon, reducing thereby asreaction ngl ucts hy rocarbons relatively poorer in y rag in, and steam.v. 3. e process of transforming parafiins and olefins into terpenes andaromatic hy drpcarbons, which consists in sub'ecting said parafl'ms andolefins, in a state 0 vapor substantially unmixe'dwith reactive oxygen,

to restricted oxidation by means of .a reducible metal oxid maintainedat asuitable temperature, producing thereby as reaction productshydrocarbons relatively hydrogen, and steam. I

4. The process of transforming paraflins poorer in drocarbons, whichconsists in sub'ecting' said parafiins and olefins, in a state 0 vaporsubstantially unmixed with reactive oxygen, to

I of subjecting mixtures. of hydrocarbons of differing boiling-point t oducting the vaporsinto contact with "a re ducible metal oxid, at-atemperature above the reduction oint of said oxid, and'pro hydrocarbonsof difierin boiling-point to restricted oxidation, which consists inprof I ,gresslvely vaporizing said mixtures, conox1d in correspondencewith the rising boil- I restricted oxidation, whic consists in pro-.gressively vaporizing said mixtures, conducting the vapors. intocontactwith ferric ox d at a temperature abovethe reduction pointthereof, and progressivelyraising the ence with the risingboiling-poi'ntof the hydrof carbons. I 7. The rprocess of transforming hydrocarbonsmto other hydrocarbons relatively oorer inhydrogen, which consists inbring mg the hydrocarbon to be transformed,'m a state of vaporsubstantially unmixed'with reactive oxygen, into contact with areducible metal oxid, and, so regulating the temperature of said oxidand the time of contact of the vapor therewith as to oxidize a part onlyofthe hydrogen component of the hydrocarbon, and toefi'ect incompletereaction, roducts hy poorer in ydrogen, and steam, .while-avoi mgmaterial separation of carbon.-

8. The process of transforming hydrooo'rer'in hy ogen, which consists inbrin roducing thereby as; ocarbo'ns' relativeliy .125 carbons intootherhydrocarbons relatively ing the hydrocarbon to be transformed, m Y

a state of vapor substantially unmixed-with reactive oxygen, intocontact with ironoxid at a temperature of 580'750 C., and so regulatin Vvapor an .the oxid as to oxidize a. part only of the hydrogen componentof the hydrocarbon, and to effect incomplete reduction of the oxid,producing thereby as reaction products hydrocarbons relatively poo rerin oxygen, to restricted oxidation by means of a reducible metal oxidmaintained at a suitable temperature, producin thereby as reactionproducts hydrocar ons relatively poorer in hydrogen, and steam, whileproviding such excess of the reducible oxid as I to avoidmaterialseparation of carbon.

10. The process of transforming paraifins and olefins into terpenes andaromatic hydrocarbons, which consists in subjecting said parafins andolefins, in a state of vapor substantially unmixed with reactive oxygen,to restricted oxidation by means of iron oxid maintained at atemperature of 580750 C. producing thereby as reaction productshydrocarbons relatively oorer in hydrogen, and steam, while provi ingsuch excess of the reducible oxid as to avoid material separation ofcarbon.

the time of contact between the' 11. The process of subjectin' mixturesof hydrocarbons of differing boi ingpoint to restricted oxidation, whichconsists in progressively vaporizing said mixtures, conducting thevapors into contact with a reducible metal oxid, at a temperature abovethe reduction point of said oxid, and progressively raising thetemperaturejof the oxid in corres ondence with the rising boiling-pointof t e hydrocarbon, While maintaining throughout the operation asufiicient excess of oxid to avoid material separation of carbon.

12. The process of subjecti'n mixtures of hydrocarbons of differing boiing-point to restricted oxidation, which consists in. progressivelyvaporizing said mixtures, conducting the vapors into contact with ferricoxid at a temperature above the reduction point thereof, andprogressively raisin the temperature of the oxid in correspon ence withthe rising boiling-point of the hydrocarbons, while maintainingthroughout the operation a sufiicient excess of oxid to avoid materialseparation of carbon.

In testimon whereof I aflix my signature in presence'o two witnesses.

ALEXANDER S. RAMAGE.

